US8563655B2 - Film of poly(trimethylene arylate)/polystyrene blends and process for making - Google Patents

Film of poly(trimethylene arylate)/polystyrene blends and process for making Download PDF

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US8563655B2
US8563655B2 US13/391,320 US201013391320A US8563655B2 US 8563655 B2 US8563655 B2 US 8563655B2 US 201013391320 A US201013391320 A US 201013391320A US 8563655 B2 US8563655 B2 US 8563655B2
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poly
polystyrene
trimethylene
film
arylate
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US20120283389A1 (en
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W. Douglas Bates
Brett Collin Dobrick
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene

Definitions

  • the present invention is directed to a film prepared from a polymer blend comprising poly(trimethylene arylate) and polystyrene.
  • Poly(trimethylene terephthalate), also known as poly(propylene terephthalate), or, less formally, as “3GT” polymer, is well known in the art. The properties and manufacturing thereof are described by Chuah in The Encyclopedia of Polymer Science , on-line, DOI 10.1002/0471440264.pst292.
  • compositions were prepared by co-feeding pellets of the two polymers into a twin screw extruder or by making a salt and pepper blend of pellets of the two polymers in the desired proportions and then feeding the resulting pellet mixture into a twin screw extruder.
  • the extrudate was extruded as a strand and chopped into pellets. These blend pellets were then fed to a spinning machine to melt spin fiber.
  • U.S. Pat. No. 4,475,330 discloses a polyester multifilament yarn made from polyester filaments consisting essentially of (a) a copolymer of two or more monomers selected from the group consisting of ethylene terephthalate, trimethylene terephthalate and tetramethylene terephthalate, and/or (b) a blend of two or more polymers of ethylene terephthalate, trimethylene terephthalate and tetramethylene terephthalate.
  • This patent describes blends of polyesters with 3 to 15% of non-crystalline polymer, preferably styrene polymers or methacrylate polymers.
  • the present invention provides a film comprising a blend of poly(trimethylene arylate) and 0.5 to 40 weight % polystyrene particles, wherein the polystyrene particles are characterized by a particle size less than 500 nm.
  • the present invention provides a process comprising combining poly(trimethylene arylate) and 0.5 to 40% by weight of polystyrene, melting the poly(trimethylene arylate) and polystyrene forming a melted poly(trimethylene arylate) and polystyrene, and melt blending the melted poly(trimethylene arylate) and polystyrene in a high shear melt mixer providing a melt blend composition comprising a poly(trimethylene arylate) and a polystyrene dispersed therewithin, conveying the melt blend composition to a film die, and extruding a film.
  • FIGS. 1 a and 1 b are schematic representations of an embodiment of a process of melt casting a film.
  • the films of the present invention exhibit improved toughness and increased opacity over films of neat poly(trimethylene arylate) polymers.
  • Poly(trimethylene arylate) polymers suitable for the practice of the invention include but are not limited to poly(trimethylene terephthalate), poly(trimethylene isophthalate), poly(trimethylene naphthalate), and mixtures and copolymers thereof.
  • the poly(trimethylene arylate) is poly(trimethylene terephthalate) (PTT).
  • PTT poly(trimethylene terephthalate)
  • PTT poly(trimethylene terephthalate)
  • the term “PTT” encompasses homopolymers and copolymers containing at least 70 mole % trimethylene terephthalate repeat units.
  • the polymer compositions are described herein in terms of weight percent (%) of ingredients based upon the total weight of polymers.
  • percentage of PS in the composition is expressed as a percentage of the total weight of the polymers, including, for example, PTT, and any other additional polymers that may be incorporated into the composition hereof.
  • copolymer shall be understood to encompass terpolymers, tetrapolymers and so forth, as well as dipolymers.
  • the present invention provides a film comprising a blend of poly(trimethylene arylate) and particles of polystyrene dispersed therewithin, the polystyrene particles being characterized by a particle size less than 500 nm.
  • the film comprises PTT and 0.5 to 40% by weight of PS dispersed therewithin.
  • the PTT is present as a continuous phase or “matrix” and the PS is a discontinuous phase dispersed within the PTT matrix.
  • the film comprises 15 to 40% by weight of PS dispersed therewithin.
  • the film comprises 20 to 30% by weight of PS dispersed therewithin.
  • the film comprises 0.5 to 5% by weight of PS.
  • the film comprises 0.5 to 1.5% by weight of PS.
  • the film comprises up to 30 weight % of other polyesters.
  • Other polyesters include but are not limited to poly(ethylene terephthalate), poly(butylene terephthalate), and poly(ethylene naphthalate).
  • the film comprises 50 to 80% of the PTT, and 20 to 30% of PS, and up to 30% of other polyesters, supra.
  • Suitable PTT polymer is formed by the condensation polymerization of 1,3-propanediol and terephthalic acid or dimethyl terephthalate.
  • One or more suitable comonomers for copolymerization therewith is selected from the group consisting of linear, cyclic, and branched aliphatic dicarboxylic acids or esters having 4-12 carbon atoms (for example butanedioic acid, pentanedioic acid, hexanedioic acid, dodecanedioic acid, 1,4-cyclohexanedicarboxylic acid, and their corresponding esters); aromatic dicarboxylic acids or esters other than terephthalic acid or ester and having 8-12 carbon atoms (for example isophthalic acid and 2,6-naphthalenedicarboxylic acid); linear, cyclic, and branched aliphatic diols having 2-8 carbon atoms (other than 1,3-propanediol
  • the PTT can contain minor amounts of other comonomers; such comonomers are usually selected so that they do not have a significant adverse affect on properties.
  • Such other comonomers include 5-sodium-sulfoisophthalate, for example, at a level in the range of about 0.2 to 5 mole %.
  • Very small amounts of trifunctional comonomers, for example trimellitic acid, can be incorporated for viscosity control.
  • the PTT can be blended with up to 30 mole percent of other polymers. Examples are polyesters prepared from other diols, such as those described supra.
  • the PTT contains at least 85 mol-% of trimethylene terephthalate repeat units. In a further embodiment, the PTT contains at least 90 mol-% of trimethylene terephthalate repeat units, In a still further embodiment the PTT contains at least 98 mol-% of trimethylene terephthalate repeat units. In a still further embodiment the PTT contains 100 mol-% of trimethylene terephthalate repeat units.
  • suitable PTT is characterized by an intrinsic viscosity (IV) in the range of 0.70 to 2.0 dl/g. In a further embodiment, suitable PTT is characterized by an IV in the range of 0.80 to 1.5 dl/g. In a still further embodiment, suitable PTT is characterized by an IV in the range of 0.90 to 1.2 dl/g.
  • IV intrinsic viscosity
  • suitable PTT is characterized by a number average molecular weight (M n ) in the range of 10,000 to 40,000 Da. In a further embodiment suitable PTT is characterized by M n in the range of 20,000 to 25,000 Da.
  • a polystyrene is selected from the group consisting of polystyrene homopolymer, ⁇ -methyl-polystyrene, and styrene-butadiene copolymers and blends thereof.
  • the polystyrene is a polystyrene homopolymer.
  • the polystyrene homopolymer is characterized by M n in the range of 5,000 to 300,000 Da.
  • M n of the polystyrene homopolymer is in the range of 50,000 to 200,000 Da.
  • M n of the polystyrene homopolymer is in the range of 75,000 to 200,000 Da. In a still further embodiment, M n of the polystyrene homopolymer is in the range of 120,000 to 150,000 Da.
  • Useful polystyrenes can be isotactic, atactic, or syndiotactic. High molecular weight atactic polystyrene is preferred.
  • Polystyrenes useful in this invention are commercially available from many suppliers including Dow Chemical Co. (Midland, Mich.), BASF (Mount Olive, N.J.) and Sigma-Aldrich (Saint Louis, Mo.).
  • PTT and PS are melt blended and, then, extruded in the form of a strand that is subsequently cut into pellets.
  • Other forms of melt blending and subsequent comminution, such as into flake, chips, or powder, can also be performed.
  • the pellets are then remelted and extruded into films, with or without with additional PTT in the melt.
  • the polymer blend comprises PTT and PS. In some embodiments these will be the only two materials in the blend and they will total 100 weight %. However, in many instances the blend will have other ingredients such as are commonly added to polyester polymers in commercial use. Such additives include but are not limited to other polymers, plasticizers, UV absorbers, flame retardants, dyestuffs, and so on. Thus, the total of the PTT and PS will be less than 100 weight %.
  • the invention provides a process comprising combining poly(trimethylene arylate) and a PS in concentration of 0.5 to 40% by weight, melting the poly(trimethylene arylate) and PS; melt blending the melted poly(trimethylene arylate) and PS in a high shear melt mixer to provide a melt composition comprising a poly(trimethylene arylate) and a PS dispersed therewithin.
  • the PTT/PS blend so produced is extruded into one or more strands about 1 ⁇ 8′′ to 3/16′′ in diameter that are then cut up into pellets.
  • pellets so produced can be employed as they are to cast films; or, if they are relatively high in PS concentration, the pellets so produced can also be employed as a concentrate or masterbatch which can be diluted in the melt by addition of neat PTT polymer.
  • both the PTT/PS composition may be in the form of chips, flakes, or powder instead of pellets.
  • pellets any or all of the alternative forms may be substituted therefor.
  • extrusion-processing performance is best when the polymeric components are fed as pellets rather than chips, flakes, or powder.
  • the PTT/PS blend is not pelletized but is directed while still in the melt to a film die from which a film is extruded, as described infra.
  • the poly(trimethylene arylate) is PTT.
  • the PS is at a concentration of 0.5% to 40% by weight.
  • the PS is at a concentration of 15% to 40% by weight
  • the PS is at a concentration of 20% to 30% by weight.
  • the PS is at a concentration of 0.5 to 5% by weight.
  • the PS is at a concentration of 0.5 to 1.5% by weight.
  • the PTT is characterized by an IV in the range of 0.90 to 1.2 dl/g.
  • the PS is PS homopolymer.
  • the PS homopolymer is characterized by a number average molecular weight of 75,000 to 200,000 Da.
  • the polystyrene is polystyrene homopolymer at a concentration of 20 to 30% and is characterized by a number average molecular weight of 75,000 to 200,000 Da;
  • the poly(trimethylene arylate) is poly(trimethylene terephthalate) comprising 98 mol-% of trimethylene terephthalate monomer units and whereof the intrinsic viscosity is in the range of 0.90 to 1.2 dl/g.
  • the PTT and PS can be melt blended by any known technique, including but not limited to an embodiment (a) comprising melting and mixing simultaneously from separate feeds, as, for example, in a co-fed twin screw extruder; an embodiment (b) comprising pre-mixing the unmelted polymers in a separate apparatus before melt blending, as, for example, in tumble blending pellets or flake of the polymers prior to feeding a twin-screw extruder, or an embodiment (c) comprising melting each polymer separately and then mixing the melts, as, for example, in feeding a twin screw extruder with the PTT in molten form from a continuous melt polymerizer, and feeding the twin-extruder with PS in molten form from a satellite single or twin screw extruder.
  • an embodiment (a) comprising melting and mixing simultaneously from separate feeds as, for example, in a co-fed twin screw extruder
  • composition hereof include, but are not limited to, the size of the PS particles formed within the PTT matrix, and the volume homogeneity of the PS particle distribution within the PTT matrix. Average particle size greater than 500 nm is not desirable from the standpoint of good film forming performance. Additionally, uniform film depends expressly upon the homogeneity of the volume distribution of the PS particles. It is expected that in the actual melt processing thereof, the PS particles melt to form molten droplets that are dispersed within a molten PTT matrix.
  • melt temperature in the melt mixer should be above the melting points of both the PTT and the PS but below the lowest decomposition temperature of any of the ingredients. Specific temperatures will depend upon the particular attributes of the polymers employed. In typical practice, melt temperature is in the range of 200° C. to 270° C.
  • Both fine particle size of PS and volume homogeneity of the dispersion of PS in the PTT depend upon the application of high shear melt blending. This is especially true for the high concentrations of PS employed in the compositions hereof.
  • the amount of shear force applied to the melt depends upon the rotational speed of the mixing elements, the viscosity of the melt, and the residence time of the melt in the mixing zone. If the shear forces are too low there is a tendency for the PS to not break up to begin with, or to agglomerate rapidly into droplets greater than 500 nm in size.
  • the melt blending process can be performed both batchwise and continuously.
  • High shear mixers such as are commonly employed in the art of polymer compounding are suitable.
  • suitable commercially available high shear batch mixers include, but are not limited to, Banbury mixers and Brabender mixers.
  • suitable continuous high shear mixers include co-rotating twin-screw extruders and Farrel Continuous Mixers Counter-rotating twin screw extruders are also suitable.
  • suitable high shear mixers are those that are capable of exerting on a polymer melt a minimum shear rate of 50/s, with 100/s preferred.
  • the polymer blend pellets Prior to melt casting film, the polymer blend pellets are dried to a moisture level of ⁇ 30 ppm to avoid hydrolytic degradation during film fabrication. Any means for drying known in the art is satisfactory. In one embodiment, a closed loop hot air dryer is employed. Typically, the PTT/PS blend is dried at 130° C. and a dew point of ⁇ 40° C. for 6 h. The thus dried PTT/PS polymer blend is melt cast at 250-265° C. into films using conventional processing machines
  • FIG. 1 a shows a schematic side view of an embodiment of the film casting process hereof.
  • FIG. 1 b shows a schematic top view.
  • the pellets so prepared are placed in a feeder, 1 , and fed to an extruder, 2 , in which the pellets are melted and conveyed to a film die, 3 , from which a film, 4 , is extruded.
  • the film, 4 is directed to a rotating water-cooled casting drum, 5 .
  • the film is held to the casting drum surface by a nip roll, 6 , and from the nip roll, is directed to a tension-controlled wind-up, 7 .
  • the direction of rotation of the various rolls is indicated by the curved arrows, 8 .
  • the direction of film movement is indicated by the arrow, 9 .
  • the air gap, 10 between the die lips and the casting drum is greatly exaggerated for purposes of illustration.
  • the extruder can be a twin screw extruder or a single screw extruder, the single screw extruder being preferred.
  • the extruder is a twin screw extruder.
  • the single feeder, 1 is replaced by two feeders, preferably weight loss feeders, one feeding PS and the other feeding PTT. The feeders are set at the respective rates necessary to achieve the desired concentration of PS.
  • the properties of the produced film are determined by the molecular weight of the PTT, the concentration of the PS, the die pressure, the die design, the die lip opening, the amount of draw-down from the die, the length of air gap, 10 , and, the temperature of the casting drum.
  • Sorona® Bright PTT resin (1.02 IV available from the DuPont Company, Wilmington, Del.) polytrimethylene terephthalate was combined with polystyrene (168 M KG 2 available from BASF) in the amounts shown in Table 1.
  • the PTT was dried in a vacuum oven with a nitrogen purge at 120° C. for 14 hours prior to use.
  • the two polymers were individually weight-loss fed to the fourth barrel section of a Werner & Pfleiderer ZSK-30 co-rotating twin screw extruder.
  • the feed rates employed are shown in Table 1 in pounds per hour (pph).
  • the extruder had a 30 mm diameter barrel constructed with 13 barrel sections provided in alternating arrangement with two kneading zones and three conveying sections, the extruder having an L/D ratio of 32. Each barrel section was independently heated. Sections 1-4 were set at 25° C., Sections 5-13 were set at 210° C., the 3/16′′ strand die was also set at 210° C. A vacuum was applied to barrel segment 8. The screw speed was as indicated in Table 1. Table 1 also shows the composition of the feed, the rate of output, and the melt temperature. The polymer was quenched in water immediately upon exiting the die and was then pelletized using standard pelletizing equipment into 1 ⁇ 8′′ pellets.
  • Sorona® Bright PTT resin (Dupont, Wilmington, Del.) was combined with 20 weight % of the polystyrene used in Examples 1-6.
  • the PTT was dried prior to use as in Examples 1-6.
  • the two polymers were independently fed by weight loss feeders at 28 pph of PTT and 7 pph PS into the 4 th barrel section of a Werner & Pfleiderer ZSK-30 co-rotating twin screw extruder provided with 13 independently heated barrel sections.
  • the throat temperature and first barrel temperature were set at 190° C., with the following 12 sections set at 210° C.
  • the polymer was extruded through a single stand die with a 3/16′′ hole.
  • the polymer strand was then water-quenched and pelletized into 1 ⁇ 8′′ pellets.
  • Example 7 0.4 lbs of the PTT/PS pellets produced in Example 7 were mixed with 9.6 lbs of Sorona® Bright PTT resin pellets containing no PS.
  • the resulting pellet mixture was fed to a Werner & Pfleiderer extruder with a 28 mm diameter barrel and 6 barrel segments each set to 240° C. Screw speed was 150 rpm.
  • a melt temperature of 268° C. was determined by hand at the exit of the extruder.
  • the extruder output was fed to a 10 inch coat hanger film die set at 239° C.
  • the die gap was set at 0.010 in and the die pressure was 296 psi.
  • a film was cast onto a water-cooled rotating casting drum, to a wind-up operating at 8 feet per minute. The prepared film was found to exhibit a uniform thickness of 0.002 in and was 10 in wide.
  • a section of the film so produced was examined by transmission electron microscopy (TEM). By visual inspection, the preponderance of PS particles were characterized

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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US13/391,320 2009-08-20 2010-08-20 Film of poly(trimethylene arylate)/polystyrene blends and process for making Expired - Fee Related US8563655B2 (en)

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4475330A (en) 1982-06-03 1984-10-09 Teijin Limited High twist polyester multifilament yarn and fabric made therefrom
JP2003020389A (ja) 2001-05-02 2003-01-24 Asahi Kasei Corp 熱可塑性樹脂組成物
CN1445280A (zh) 2003-04-11 2003-10-01 山东大学 聚对苯二甲酸丙二醇酯类热可塑性树脂组合物及其成型品
US20040009352A1 (en) 2002-07-11 2004-01-15 Chang Jing C. Poly(trimethylene terephthalate) fibers, their manufacture and use
US20040066556A1 (en) 2002-10-07 2004-04-08 Eastman Kodak Company Voided polymer film containing layered particulates
US20040121151A1 (en) 2002-12-19 2004-06-24 Chang Jing C. Poly(trimethylene dicarboxylate) fibers, their manufacture and use
US6923925B2 (en) 2002-06-27 2005-08-02 E. I. Du Pont De Nemours And Company Process of making poly (trimethylene dicarboxylate) fibers
US20120296043A1 (en) * 2009-08-20 2012-11-22 E. I. Du Pont De Nemours And Company Poly(trimethylene arylate)/polystyrene composition and process for preparing
US20120292808A1 (en) * 2009-08-20 2012-11-22 E. I. Du Pont De Nemours And Company Process for producing shaped articles of poly(trimethylene arylate)/polystyrene

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4475330A (en) 1982-06-03 1984-10-09 Teijin Limited High twist polyester multifilament yarn and fabric made therefrom
JP2003020389A (ja) 2001-05-02 2003-01-24 Asahi Kasei Corp 熱可塑性樹脂組成物
US6923925B2 (en) 2002-06-27 2005-08-02 E. I. Du Pont De Nemours And Company Process of making poly (trimethylene dicarboxylate) fibers
US20040009352A1 (en) 2002-07-11 2004-01-15 Chang Jing C. Poly(trimethylene terephthalate) fibers, their manufacture and use
US20040066556A1 (en) 2002-10-07 2004-04-08 Eastman Kodak Company Voided polymer film containing layered particulates
US20040121151A1 (en) 2002-12-19 2004-06-24 Chang Jing C. Poly(trimethylene dicarboxylate) fibers, their manufacture and use
CN1445280A (zh) 2003-04-11 2003-10-01 山东大学 聚对苯二甲酸丙二醇酯类热可塑性树脂组合物及其成型品
US20120296043A1 (en) * 2009-08-20 2012-11-22 E. I. Du Pont De Nemours And Company Poly(trimethylene arylate)/polystyrene composition and process for preparing
US20120292808A1 (en) * 2009-08-20 2012-11-22 E. I. Du Pont De Nemours And Company Process for producing shaped articles of poly(trimethylene arylate)/polystyrene

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TW201125914A (en) 2011-08-01
CN102482470A (zh) 2012-05-30
WO2011022630A1 (en) 2011-02-24

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